2-[5-(4-Bromo­phen­yl)-3-methyl­sulfanyl-1-benzofuran-2-yl]acetic acid

Choi, H.D.; Seo, P.J.; Son, B.W.; Lee, U.

doi:10.1107/S1600536807049926

2-[5-(4-Bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid

H. D. Choi, P. J. Seo, B. W. Son and U. Lee

The title compound, C₁₇H₁₃BrO₃S, was prepared by alkaline hydrolysis of ethyl 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate. There are two symmetry-independent molecules in the asymmetric unit. The 4-bromophenyl rings are rotated out of the benzofuran planes, with dihedral angles for the two molecules of 50.22 (8) and 35.4 (1)°. The methyl groups of the methylsulfanyl substituent are almost perpendicular to the plane of the benzofuran fragment [99.5 (2) and 100.8 (2)°] and are slightly tilted towards it. The crystal structure is stabilized by a C—H

O hydrogen bond and a Br

O halogen bond [Br

O = 3.284 (2) Å], and by inversion-related intermolecular O—H

O hydrogen bonds between the carboxyl groups from two symmetry-independent molecules.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807049926/sj2376sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807049926/sj2376Isup2.hkl Contains datablock I

CCDC reference: 667366

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Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.004 Å
R factor = 0.041
wR factor = 0.113
Data-to-parameter ratio = 16.9

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Alert level C
PLAT142_ALERT_4_C su on b - Axis Small or Missing (x 100000) .....         10 Ang.
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        100 Deg.
PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 =          5

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
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Comment top

As part of our ongoing studies on the synthesis and structure of 2-(5-aryl-3-methylsulfanyl-1-benzofuran-2-yl)acetic acid derivatives, we have recently described ethyl 2-[5-(4-hydroxyphenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (Choi et al., 2006) and 2-(3-methylsulfanyl-5-phenyl-1-benzofuran-2-yl)acetic acid (Choi et al., 2007). Herein we report the molecular and crystal structure of the title compound, 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid which crystallizes with two unique molecules, A & B, in the asymmetric unit (Fig. 1).

The benzofuran unit is essentially planar, with a mean deviation of 0.019 Å, for A, and 0.013 Å, for B, respectively, from the least-squares plane defined by the nine constituent atoms. In the title compound, the dihedral angles formed by the plane of the benzofuran and the plane of the 4-bromophenyl ring are 50.22 (8)° in A and 35.4 (1)° in B, respectively. The methyl groups (S1—CH₃ in A and S2—CH₃ in B) are tilted towards the plane of the benzofuran systems [99.5 (2)°, A and 100.8 (2)°, B]. The molecular packing (Fig. 2) is stabilized by a C—H···O hydrogen bond (Table 1 and Fig. 2), between a methyl H and the C═O unit, i.e. C17—H17B···O2ⁱ. Further stability comes from a weak Br···O interaction (Fig. 2) (Politzer et al., 2007) between the bromine atom and the oxygen of a neighbouring C═O unit, with a Br2···O6ⁱⁱ distance of 3.284 (2) Å (Symmetry codes as in Fig. 2). Classical inversion-related O3—H35···O5ⁱ and O6—H36···O2ⁱ hydrogen bonds link the carboxyl groups from two symmetry-independent molecules (Table 1 and Fig. 2).

Related literature top

For the crystal structures of similar benzofuran compounds, see: Choi et al. (2006, 2007). For a review of halogen bonding, see: Politzer, et al. (2007).

Experimental top

Ethyl 2-[5-(4-bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetate (729 mg, 1.8 mmol) was added to a solution of potassium hydroxide (561 mg, 10.0 mmol) in water (15 ml) and methanol (15 ml), and the mixture was heated at 343 K for 4 h, then cooled. Water was added, and the solution was washed with chloroform. The aqueous layer was acidified to pH 1 with concentrated hydrochloric acid and then extracted with chloroform, dried over magnesium sulfate, filtered and concentrated under vacuum. The residue was purified by column chromatography (ethyl acetate) to afford the title compound as a colorless solid [yield 87%, m.p. 476–477 K; R_f = 0.81 (ethyl acetate)]. Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a dilute solution of the title compound in acetone at room temperature.

Structure description top

For the crystal structures of similar benzofuran compounds, see: Choi et al. (2006, 2007). For a review of halogen bonding, see: Politzer, et al. (2007).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The O—H···O and C—H···O hydrogen bonds, and Br···O halogen bond (dotted lines) in the title compound. [Symmetry codes: (i) 3 - x, -y, -z; (ii) 2 - x, 1 - y, 1 - z.]

2-[5-(4-Bromophenyl)-3-methylsulfanyl-1-benzofuran-2-yl]acetic acid top

Crystal data top

C₁₇H₁₃BrO₃S	Z = 4
M_r = 377.24	F(000) = 760
Triclinic, P1	D_x = 1.580 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.7531 (1) Å	Cell parameters from 6878 reflections
b = 10.8299 (1) Å	θ = 2.4–26.1°
c = 19.5621 (2) Å	µ = 2.73 mm⁻¹
α = 104.131 (1)°	T = 298 K
β = 93.631 (1)°	Block, colourless
γ = 92.870 (1)°	0.40 × 0.22 × 0.17 mm
V = 1585.99 (3) Å³

Data collection top

Bruker SMART CCD diffractometer	6889 independent reflections
Radiation source: fine-focus sealed tube	5128 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.019
Detector resolution: 10.0 pixels mm^-1	θ_max = 27.0°, θ_min = 1.1°
φ and ω scans	h = −9→7
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	k = −13→13
T_min = 0.482, T_max = 0.637	l = −24→24
29666 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0468P)² + 1.5959P] where P = (F_o² + 2F_c²)/3
6889 reflections	(Δ/σ)_max < 0.001
407 parameters	Δρ_max = 0.98 e Å⁻³
0 restraints	Δρ_min = −0.82 e Å⁻³

Crystal data top

C₁₇H₁₃BrO₃S	γ = 92.870 (1)°
M_r = 377.24	V = 1585.99 (3) Å³
Triclinic, P1	Z = 4
a = 7.7531 (1) Å	Mo Kα radiation
b = 10.8299 (1) Å	µ = 2.73 mm⁻¹
c = 19.5621 (2) Å	T = 298 K
α = 104.131 (1)°	0.40 × 0.22 × 0.17 mm
β = 93.631 (1)°

Data collection top

Bruker SMART CCD diffractometer	6889 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2000)	5128 reflections with I > 2σ(I)
T_min = 0.482, T_max = 0.637	R_int = 0.019
29666 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.113	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.98 e Å⁻³
6889 reflections	Δρ_min = −0.82 e Å⁻³
407 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Br1	0.60522 (6)	0.18122 (4)	0.49776 (2)	0.07480 (15)
Br2	0.76860 (7)	0.72243 (5)	0.72068 (2)	0.08609 (17)
S1	1.25540 (10)	0.03549 (8)	0.06637 (5)	0.0514 (2)
S2	1.33833 (11)	0.73058 (10)	0.28286 (5)	0.0626 (2)
O1	0.9335 (3)	−0.27217 (19)	0.00294 (10)	0.0443 (5)
O2	1.3988 (3)	−0.2684 (2)	−0.12497 (12)	0.0577 (6)
O3	1.3216 (4)	−0.3477 (3)	−0.03577 (14)	0.0674 (7)
H35	1.406 (8)	−0.389 (5)	−0.045 (3)	0.13 (2)*
O4	0.9304 (3)	0.5069 (2)	0.18828 (11)	0.0527 (5)
O5	1.4056 (3)	0.4862 (2)	0.06232 (12)	0.0558 (6)
O6	1.3168 (4)	0.3951 (3)	0.14457 (13)	0.0630 (7)
H36	1.391 (6)	0.358 (4)	0.135 (2)	0.087 (16)*
C1	1.0950 (4)	−0.0895 (3)	0.05385 (15)	0.0388 (6)
C2	0.9754 (3)	−0.1131 (3)	0.10368 (15)	0.0378 (6)
C3	0.9381 (4)	−0.0489 (3)	0.17147 (14)	0.0394 (6)
H3	0.9978	0.0282	0.1945	0.047*
C4	0.8100 (4)	−0.1024 (3)	0.20400 (15)	0.0404 (6)
C5	0.7238 (4)	−0.2198 (3)	0.16914 (16)	0.0457 (7)
H5	0.6416	−0.2561	0.1923	0.055*
C6	0.7572 (4)	−0.2834 (3)	0.10136 (16)	0.0467 (7)
H6	0.6983	−0.3606	0.0781	0.056*
C7	0.8821 (4)	−0.2261 (3)	0.07034 (14)	0.0394 (6)
C8	1.0620 (4)	−0.1855 (3)	−0.00486 (15)	0.0413 (6)
C9	0.7624 (4)	−0.0338 (3)	0.27527 (15)	0.0430 (6)
C10	0.7279 (5)	0.0940 (3)	0.28954 (17)	0.0544 (8)
H10	0.7366	0.1374	0.2542	0.065*
C11	0.6808 (5)	0.1584 (3)	0.35513 (18)	0.0584 (8)
H11	0.6566	0.2439	0.3637	0.070*
C12	0.6703 (4)	0.0941 (3)	0.40722 (16)	0.0511 (8)
C13	0.7044 (4)	−0.0320 (3)	0.39538 (17)	0.0547 (8)
H13	0.6977	−0.0741	0.4314	0.066*
C14	0.7491 (4)	−0.0962 (3)	0.32900 (16)	0.0501 (7)
H14	0.7704	−0.1822	0.3205	0.060*
C15	1.1362 (4)	−0.2090 (3)	−0.07483 (16)	0.0470 (7)
H15A	1.1598	−0.1275	−0.0859	0.056*
H15B	1.0499	−0.2580	−0.1105	0.056*
C16	1.2989 (4)	−0.2782 (3)	−0.07950 (15)	0.0430 (6)
C17	1.4235 (5)	−0.0275 (5)	0.1136 (3)	0.0887 (14)
H17A	1.3829	−0.0393	0.1571	0.133*
H17B	1.5241	0.0313	0.1237	0.133*
H17C	1.4530	−0.1079	0.0851	0.133*
C18	1.1413 (4)	0.6404 (3)	0.25681 (16)	0.0467 (7)
C19	1.0116 (4)	0.6135 (3)	0.30190 (15)	0.0413 (6)
C20	0.9929 (4)	0.6474 (3)	0.37435 (15)	0.0428 (6)
H20	1.0772	0.7006	0.4051	0.051*
C21	0.8478 (4)	0.6011 (3)	0.39999 (15)	0.0455 (7)
C22	0.7219 (4)	0.5223 (3)	0.35249 (18)	0.0576 (8)
H22	0.6235	0.4931	0.3702	0.069*
C23	0.7373 (5)	0.4859 (4)	0.28023 (18)	0.0608 (9)
H23	0.6527	0.4335	0.2492	0.073*
C24	0.8854 (4)	0.5322 (3)	0.25728 (16)	0.0475 (7)
C25	1.0861 (4)	0.5761 (3)	0.19068 (16)	0.0467 (7)
C26	0.8272 (4)	0.6325 (3)	0.47745 (16)	0.0467 (7)
C27	0.8862 (4)	0.7505 (3)	0.52105 (16)	0.0520 (8)
H27	0.9382	0.8116	0.5015	0.062*
C28	0.8687 (5)	0.7789 (3)	0.59368 (18)	0.0584 (8)
H28	0.9078	0.8584	0.6224	0.070*
C29	0.7931 (5)	0.6879 (4)	0.62205 (17)	0.0578 (9)
C30	0.7355 (5)	0.5696 (4)	0.58056 (19)	0.0605 (9)
H30	0.6859	0.5083	0.6007	0.073*
C31	0.7523 (5)	0.5428 (3)	0.50844 (18)	0.0576 (8)
H31	0.7125	0.4630	0.4802	0.069*
C32	1.1614 (4)	0.5649 (3)	0.12150 (16)	0.0518 (8)
H32A	1.2035	0.6493	0.1188	0.062*
H32B	1.0700	0.5345	0.0841	0.062*
C33	1.3073 (4)	0.4775 (3)	0.10812 (14)	0.0415 (6)
C34	1.2640 (6)	0.8890 (4)	0.3101 (3)	0.0804 (12)
H34A	1.1966	0.9078	0.2715	0.121*
H34B	1.3620	0.9499	0.3241	0.121*
H34C	1.1939	0.8938	0.3493	0.121*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0754 (3)	0.0850 (3)	0.0525 (2)	−0.0104 (2)	0.02318 (18)	−0.00634 (18)
Br2	0.0983 (3)	0.1191 (4)	0.0429 (2)	0.0032 (3)	0.0189 (2)	0.0216 (2)
S1	0.0423 (4)	0.0513 (4)	0.0666 (5)	−0.0002 (3)	0.0061 (4)	0.0262 (4)
S2	0.0398 (4)	0.0817 (6)	0.0665 (5)	0.0022 (4)	0.0152 (4)	0.0164 (5)
O1	0.0474 (12)	0.0433 (11)	0.0421 (11)	0.0041 (9)	0.0105 (9)	0.0083 (8)
O2	0.0580 (14)	0.0611 (14)	0.0626 (14)	0.0147 (11)	0.0258 (11)	0.0244 (11)
O3	0.0770 (18)	0.0798 (18)	0.0624 (15)	0.0411 (15)	0.0278 (13)	0.0375 (13)
O4	0.0582 (14)	0.0560 (13)	0.0403 (11)	0.0047 (11)	0.0111 (10)	0.0031 (9)
O5	0.0593 (14)	0.0645 (14)	0.0569 (13)	0.0217 (11)	0.0290 (11)	0.0306 (11)
O6	0.0748 (18)	0.0715 (16)	0.0590 (15)	0.0333 (14)	0.0339 (13)	0.0346 (13)
C1	0.0353 (14)	0.0411 (15)	0.0443 (15)	0.0077 (11)	0.0068 (12)	0.0170 (12)
C2	0.0332 (14)	0.0406 (15)	0.0422 (14)	0.0043 (11)	0.0034 (11)	0.0148 (12)
C3	0.0388 (15)	0.0400 (15)	0.0401 (14)	0.0029 (12)	0.0010 (12)	0.0117 (12)
C4	0.0396 (15)	0.0446 (16)	0.0399 (14)	0.0094 (12)	0.0057 (12)	0.0139 (12)
C5	0.0409 (16)	0.0488 (17)	0.0508 (17)	0.0038 (13)	0.0128 (13)	0.0162 (14)
C6	0.0452 (17)	0.0413 (16)	0.0529 (17)	−0.0023 (13)	0.0079 (14)	0.0105 (13)
C7	0.0397 (15)	0.0419 (15)	0.0372 (14)	0.0073 (12)	0.0061 (11)	0.0093 (12)
C8	0.0413 (16)	0.0433 (15)	0.0453 (15)	0.0128 (12)	0.0112 (12)	0.0186 (13)
C9	0.0374 (15)	0.0530 (17)	0.0406 (15)	0.0062 (13)	0.0052 (12)	0.0140 (13)
C10	0.070 (2)	0.0508 (18)	0.0448 (17)	0.0076 (16)	0.0078 (15)	0.0150 (14)
C11	0.069 (2)	0.0480 (18)	0.0548 (19)	0.0068 (16)	0.0102 (17)	0.0042 (15)
C12	0.0441 (17)	0.063 (2)	0.0410 (16)	−0.0003 (14)	0.0096 (13)	0.0020 (14)
C13	0.0520 (19)	0.072 (2)	0.0450 (17)	0.0044 (16)	0.0122 (14)	0.0217 (16)
C14	0.0503 (18)	0.0548 (18)	0.0506 (17)	0.0131 (14)	0.0132 (14)	0.0190 (14)
C15	0.0512 (18)	0.0527 (17)	0.0426 (15)	0.0147 (14)	0.0102 (13)	0.0182 (13)
C16	0.0505 (17)	0.0404 (15)	0.0404 (15)	0.0080 (13)	0.0119 (13)	0.0114 (12)
C17	0.057 (2)	0.092 (3)	0.126 (4)	−0.009 (2)	−0.028 (2)	0.056 (3)
C18	0.0409 (16)	0.0550 (18)	0.0450 (16)	0.0101 (13)	0.0128 (13)	0.0100 (13)
C19	0.0365 (15)	0.0447 (15)	0.0432 (15)	0.0091 (12)	0.0116 (12)	0.0084 (12)
C20	0.0400 (15)	0.0469 (16)	0.0399 (15)	0.0054 (12)	0.0070 (12)	0.0065 (12)
C21	0.0444 (17)	0.0496 (17)	0.0429 (16)	0.0065 (13)	0.0110 (13)	0.0097 (13)
C22	0.0489 (19)	0.067 (2)	0.0546 (19)	−0.0065 (16)	0.0157 (15)	0.0094 (16)
C23	0.054 (2)	0.069 (2)	0.0516 (19)	−0.0123 (17)	0.0082 (15)	0.0011 (16)
C24	0.0515 (18)	0.0481 (17)	0.0407 (15)	0.0061 (14)	0.0102 (13)	0.0046 (13)
C25	0.0475 (17)	0.0493 (17)	0.0460 (16)	0.0162 (14)	0.0160 (13)	0.0112 (13)
C26	0.0427 (16)	0.0531 (18)	0.0464 (16)	0.0085 (13)	0.0137 (13)	0.0126 (14)
C27	0.0568 (19)	0.0534 (18)	0.0465 (17)	0.0010 (15)	0.0106 (14)	0.0128 (14)
C28	0.063 (2)	0.063 (2)	0.0476 (18)	0.0027 (17)	0.0095 (16)	0.0091 (16)
C29	0.057 (2)	0.080 (2)	0.0408 (17)	0.0138 (18)	0.0131 (15)	0.0187 (17)
C30	0.064 (2)	0.068 (2)	0.057 (2)	0.0071 (18)	0.0176 (17)	0.0276 (18)
C31	0.063 (2)	0.0557 (19)	0.0552 (19)	0.0024 (16)	0.0165 (16)	0.0135 (15)
C32	0.060 (2)	0.0585 (19)	0.0417 (16)	0.0217 (16)	0.0171 (14)	0.0144 (14)
C33	0.0471 (16)	0.0445 (16)	0.0335 (14)	0.0076 (13)	0.0082 (12)	0.0085 (12)
C34	0.065 (3)	0.069 (3)	0.105 (3)	−0.006 (2)	−0.009 (2)	0.024 (2)

Geometric parameters (Å, º) top

Br1—C12	1.904 (3)	C13—H13	0.9300
Br2—C29	1.897 (3)	C14—H14	0.9300
Br2—O6ⁱ	3.284 (2)	C15—C16	1.496 (4)
S1—C1	1.752 (3)	C15—H15A	0.9700
S1—C17	1.806 (4)	C15—H15B	0.9700
S2—C18	1.748 (3)	C17—H17A	0.9600
S2—C34	1.804 (4)	C17—H17B	0.9600
O1—C8	1.376 (3)	C17—H17C	0.9600
O1—C7	1.382 (3)	C18—C25	1.342 (4)
O2—C16	1.236 (3)	C18—C19	1.443 (4)
O3—C16	1.279 (4)	C19—C24	1.387 (4)
O3—H35	0.82 (6)	C19—C20	1.393 (4)
O4—C25	1.381 (4)	C20—C21	1.381 (4)
O4—C24	1.381 (3)	C20—H20	0.9300
O5—C33	1.230 (3)	C21—C22	1.399 (5)
O6—C33	1.273 (4)	C21—C26	1.490 (4)
O6—H36	0.73 (5)	C22—C23	1.386 (5)
C1—C8	1.348 (4)	C22—H22	0.9300
C1—C2	1.445 (4)	C23—C24	1.375 (5)
C2—C7	1.382 (4)	C23—H23	0.9300
C2—C3	1.394 (4)	C25—C32	1.488 (4)
C3—C4	1.388 (4)	C26—C31	1.387 (4)
C3—H3	0.9300	C26—C27	1.389 (4)
C4—C5	1.401 (4)	C27—C28	1.395 (4)
C4—C9	1.490 (4)	C27—H27	0.9300
C5—C6	1.384 (4)	C28—C29	1.368 (5)
C5—H5	0.9300	C28—H28	0.9300
C6—C7	1.374 (4)	C29—C30	1.374 (5)
C6—H6	0.9300	C30—C31	1.385 (5)
C8—C15	1.488 (4)	C30—H30	0.9300
C9—C10	1.386 (4)	C31—H31	0.9300
C9—C14	1.388 (4)	C32—C33	1.506 (4)
C10—C11	1.384 (4)	C32—H32A	0.9700
C10—H10	0.9300	C32—H32B	0.9700
C11—C12	1.372 (5)	C34—H34A	0.9600
C11—H11	0.9300	C34—H34B	0.9600
C12—C13	1.371 (5)	C34—H34C	0.9600
C13—C14	1.389 (4)

C1—S1—C17	99.5 (2)	S1—C17—H17C	109.5
C18—S2—C34	100.8 (2)	H17A—C17—H17C	109.5
C8—O1—C7	105.4 (2)	H17B—C17—H17C	109.5
C16—O3—H35	109 (4)	C25—C18—C19	106.5 (3)
C25—O4—C24	105.5 (2)	C25—C18—S2	126.2 (2)
C33—O6—H36	110 (4)	C19—C18—S2	127.2 (2)
C8—C1—C2	106.2 (2)	C24—C19—C20	119.2 (3)
C8—C1—S1	126.0 (2)	C24—C19—C18	105.6 (3)
C2—C1—S1	127.8 (2)	C20—C19—C18	135.1 (3)
C7—C2—C3	119.3 (2)	C21—C20—C19	119.3 (3)
C7—C2—C1	105.6 (2)	C21—C20—H20	120.4
C3—C2—C1	135.0 (3)	C19—C20—H20	120.4
C4—C3—C2	118.7 (3)	C20—C21—C22	119.2 (3)
C4—C3—H3	120.7	C20—C21—C26	120.4 (3)
C2—C3—H3	120.7	C22—C21—C26	120.4 (3)
C3—C4—C5	119.9 (3)	C23—C22—C21	122.9 (3)
C3—C4—C9	120.0 (3)	C23—C22—H22	118.5
C5—C4—C9	120.1 (3)	C21—C22—H22	118.5
C6—C5—C4	122.1 (3)	C24—C23—C22	115.8 (3)
C6—C5—H5	119.0	C24—C23—H23	122.1
C4—C5—H5	119.0	C22—C23—H23	122.1
C7—C6—C5	116.3 (3)	C23—C24—O4	126.1 (3)
C7—C6—H6	121.8	C23—C24—C19	123.5 (3)
C5—C6—H6	121.8	O4—C24—C19	110.4 (3)
C6—C7—C2	123.7 (3)	C18—C25—O4	112.1 (2)
C6—C7—O1	125.8 (3)	C18—C25—C32	132.4 (3)
C2—C7—O1	110.6 (2)	O4—C25—C32	115.6 (3)
C1—C8—O1	112.1 (2)	C31—C26—C27	118.0 (3)
C1—C8—C15	131.0 (3)	C31—C26—C21	120.6 (3)
O1—C8—C15	116.9 (3)	C27—C26—C21	121.4 (3)
C10—C9—C14	118.1 (3)	C26—C27—C28	121.2 (3)
C10—C9—C4	120.9 (3)	C26—C27—H27	119.4
C14—C9—C4	121.0 (3)	C28—C27—H27	119.4
C11—C10—C9	121.5 (3)	C29—C28—C27	119.0 (3)
C11—C10—H10	119.2	C29—C28—H28	120.5
C9—C10—H10	119.2	C27—C28—H28	120.5
C12—C11—C10	118.8 (3)	C28—C29—C30	121.3 (3)
C12—C11—H11	120.6	C28—C29—Br2	120.2 (3)
C10—C11—H11	120.6	C30—C29—Br2	118.4 (3)
C13—C12—C11	121.4 (3)	C29—C30—C31	119.2 (3)
C13—C12—Br1	119.2 (2)	C29—C30—H30	120.4
C11—C12—Br1	119.4 (3)	C31—C30—H30	120.4
C12—C13—C14	119.2 (3)	C30—C31—C26	121.4 (3)
C12—C13—H13	120.4	C30—C31—H31	119.3
C14—C13—H13	120.4	C26—C31—H31	119.3
C9—C14—C13	120.9 (3)	C25—C32—C33	115.1 (3)
C9—C14—H14	119.6	C25—C32—H32A	108.5
C13—C14—H14	119.6	C33—C32—H32A	108.5
C8—C15—C16	114.9 (2)	C25—C32—H32B	108.5
C8—C15—H15A	108.6	C33—C32—H32B	108.5
C16—C15—H15A	108.6	H32A—C32—H32B	107.5
C8—C15—H15B	108.6	O5—C33—O6	124.0 (3)
C16—C15—H15B	108.6	O5—C33—C32	119.5 (3)
H15A—C15—H15B	107.5	O6—C33—C32	116.4 (3)
O2—C16—O3	124.4 (3)	S2—C34—H34A	109.5
O2—C16—C15	119.7 (3)	S2—C34—H34B	109.5
O3—C16—C15	115.9 (3)	H34A—C34—H34B	109.5
S1—C17—H17A	109.5	S2—C34—H34C	109.5
S1—C17—H17B	109.5	H34A—C34—H34C	109.5
H17A—C17—H17B	109.5	H34B—C34—H34C	109.5

C17—S1—C1—C8	−97.1 (3)	C34—S2—C18—C25	113.1 (3)
C17—S1—C1—C2	81.3 (3)	C34—S2—C18—C19	−71.2 (3)
C8—C1—C2—C7	1.8 (3)	C25—C18—C19—C24	0.1 (3)
S1—C1—C2—C7	−176.9 (2)	S2—C18—C19—C24	−176.3 (2)
C8—C1—C2—C3	−177.0 (3)	C25—C18—C19—C20	178.4 (3)
S1—C1—C2—C3	4.3 (5)	S2—C18—C19—C20	2.0 (5)
C7—C2—C3—C4	1.3 (4)	C24—C19—C20—C21	−1.0 (4)
C1—C2—C3—C4	180.0 (3)	C18—C19—C20—C21	−179.1 (3)
C2—C3—C4—C5	1.3 (4)	C19—C20—C21—C22	−0.7 (4)
C2—C3—C4—C9	−177.6 (2)	C19—C20—C21—C26	178.0 (3)
C3—C4—C5—C6	−2.5 (4)	C20—C21—C22—C23	1.3 (5)
C9—C4—C5—C6	176.4 (3)	C26—C21—C22—C23	−177.4 (3)
C4—C5—C6—C7	1.1 (4)	C21—C22—C23—C24	−0.1 (6)
C5—C6—C7—C2	1.6 (4)	C22—C23—C24—O4	178.6 (3)
C5—C6—C7—O1	−179.0 (3)	C22—C23—C24—C19	−1.8 (5)
C3—C2—C7—C6	−2.8 (4)	C25—O4—C24—C23	178.5 (3)
C1—C2—C7—C6	178.2 (3)	C25—O4—C24—C19	−1.1 (3)
C3—C2—C7—O1	177.7 (2)	C20—C19—C24—C23	2.4 (5)
C1—C2—C7—O1	−1.4 (3)	C18—C19—C24—C23	−179.0 (3)
C8—O1—C7—C6	−179.1 (3)	C20—C19—C24—O4	−178.0 (3)
C8—O1—C7—C2	0.4 (3)	C18—C19—C24—O4	0.6 (3)
C2—C1—C8—O1	−1.7 (3)	C19—C18—C25—O4	−0.8 (3)
S1—C1—C8—O1	177.03 (19)	S2—C18—C25—O4	175.7 (2)
C2—C1—C8—C15	176.2 (3)	C19—C18—C25—C32	−179.9 (3)
S1—C1—C8—C15	−5.1 (5)	S2—C18—C25—C32	−3.4 (5)
C7—O1—C8—C1	0.8 (3)	C24—O4—C25—C18	1.2 (3)
C7—O1—C8—C15	−177.4 (2)	C24—O4—C25—C32	−179.6 (3)
C3—C4—C9—C10	49.0 (4)	C20—C21—C26—C31	−143.1 (3)
C5—C4—C9—C10	−129.9 (3)	C22—C21—C26—C31	35.7 (5)
C3—C4—C9—C14	−131.8 (3)	C20—C21—C26—C27	35.2 (4)
C5—C4—C9—C14	49.3 (4)	C22—C21—C26—C27	−146.0 (3)
C14—C9—C10—C11	−0.3 (5)	C31—C26—C27—C28	−0.8 (5)
C4—C9—C10—C11	178.9 (3)	C21—C26—C27—C28	−179.2 (3)
C9—C10—C11—C12	0.8 (5)	C26—C27—C28—C29	0.5 (5)
C10—C11—C12—C13	−0.4 (5)	C27—C28—C29—C30	0.4 (5)
C10—C11—C12—Br1	−179.9 (3)	C27—C28—C29—Br2	179.5 (3)
C11—C12—C13—C14	−0.5 (5)	C28—C29—C30—C31	−0.9 (6)
Br1—C12—C13—C14	178.9 (2)	Br2—C29—C30—C31	180.0 (3)
C10—C9—C14—C13	−0.7 (5)	C29—C30—C31—C26	0.5 (5)
C4—C9—C14—C13	−179.9 (3)	C27—C26—C31—C30	0.3 (5)
C12—C13—C14—C9	1.1 (5)	C21—C26—C31—C30	178.7 (3)
C1—C8—C15—C16	86.6 (4)	C18—C25—C32—C33	77.1 (4)
O1—C8—C15—C16	−95.7 (3)	O4—C25—C32—C33	−102.0 (3)
C8—C15—C16—O2	−157.5 (3)	C25—C32—C33—O5	−161.6 (3)
C8—C15—C16—O3	24.2 (4)	C25—C32—C33—O6	20.5 (4)

Symmetry code: (i) −x+2, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O3—H35···O5ⁱⁱ	0.82 (6)	1.84 (6)	2.659 (3)	176 (6)
O6—H36···O2ⁱⁱ	0.73 (5)	1.93 (5)	2.655 (3)	172 (5)
C17—H17B···O2ⁱⁱ	0.96	2.60	3.374 (5)	138

Symmetry code: (ii) −x+3, −y, −z.

Experimental details

Crystal data
Chemical formula	C₁₇H₁₃BrO₃S
M_r	377.24
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.7531 (1), 10.8299 (1), 19.5621 (2)
α, β, γ (°)	104.131 (1), 93.631 (1), 92.870 (1)
V (Å³)	1585.99 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.73
Crystal size (mm)	0.40 × 0.22 × 0.17

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 2000)
T_min, T_max	0.482, 0.637
No. of measured, independent and observed [I > 2σ(I)] reflections	29666, 6889, 5128
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.113, 1.02
No. of reflections	6889
No. of parameters	407
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.98, −0.82

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998).